Preparation of a Macrocyclic Polyamine-bonded Column for the Electrophoretic Separation of Inorganic and Organic Anions

Abstract

A 24-membered macrocyclic polyamine based on the propylene-1,3-diamine unit that was able to form polyprotonated, highly charged species in the neutral pH region was selected to act as an anion complexone. It was synthesized and incorporated in a fused-silica capillary for the electrophoretic separation of inorganic and organic anions. This complexing agent can selectively modulate the mobility of anions by forming anion complexes with varying degrees of stability. Parameters which influence capillary electrophoretic separations such as applied voltage, choice of electrolyte anion, electrolyte pH and electrolyte concentration were investigated. A mixture of thiosulfate, chloride, sulfate, selenate, perchlorate, tungstate, carbonate and selenite could be separated in 5 mm sodium chromate at pH 10.0 within 13 min. A mixture of bromide, oxalate, malate, citrate, tartrate, maleate, succinate, acetate, lactate, butyrate, p-hydroxybenzoate, salicylate and octanesulfonate could be separated in 10 mm phthalate at pH 5.0 within 11 mins. Under the same conditions, even geometric isomers or mixtures of polycarboxylates and polyphosphates, such as ATP and ADP, could be well separated. The experimental results indicated that incorporating the chelating functional group in the inner wall of the capillary markedly enhances the selectivity of the system.

Capillary electrochromatographic analysis of aliphatic mono‐ and polycarboxylic acids

“…In this system a rather low detection limit, 5-10 nM and a wider linear range, 0.05-2 mM were indicated. By comparison with Hsu's work [18], a more satisfactory result was obtained. It was also clear that 28ane-N 6 O 2 had a greater affinity and higher selectivity than 24ane-N 6 O 2 for the polycarboxylate coordination.…”

“…In a previous paper, we reported the preparation of macrocyclic polyamine-bonded phases for the electrophoretic separation of organic and inorganic anions [18,19]. Based on the multiple modes separation mechanism, a number of analytes, including aromatic organic acids [20], metal ion speciation [21] and nucleotides [22] could be well separated.…”

Macrocyclic polyamine‐modified poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) monolith for capillary electrochromatography

“…To date, extensive studies focusing on macrocyclic polyamines as the stationary phase for open-tubular CEC (OT-CEC) have been carried out by Liu et al They have bonded 24-, 28-, and 32-membered macrocyclic polyamines directly to the inner wall of the capillary to separate carbohydrates [17], nucleoside monophosphates [18], metal ion species [19], aliphatic acids [20], etc. We have demonstrated the preparation of a novel macrocyclic polyamine(dioxo [13]aneN 4 )-modified OT-CEC column via sol-gel technology [21]. However, macrocyclic polyamine as the bonded phase for monolithic columns has received scant attention.…”

“…Their outstanding capacity as inclusion-complexing agents has resulted in wide applications in analytical chemistry. 1,4,10,13,16-Pentaazatricycloheneicosane-9,17-dione (macrocyclic polyamine), another kind of macromolecules, which have similar structures to crown ethers, are well-known host compounds for the recognition of cations and anions [12,13]. Although macrocyclic polyamines have found many applications in various fields of analytical chemistry, reports concerning the utility of macrocyclic polyamines in chromatographic separations are limited [14][15][16][17][18][19][20][21], especially in CEC [16][17][18][19][20][21].…”

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Macrocyclic polyamine-modified poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith for capillary electrochromatography 1,4,10,13,,17-dione (macrocyclic polyamine)-modified polymer-based monolithic column for CEC was prepared by ring opening reaction of epoxide groups from poly(glycidyl methacrylate-co-ethylene dimethacrylate) (GMA-co-EDMA) monolith with macrocyclic polyamine. Conditions such as reaction time and concentration of macrocyclic polyamine for the modification reaction were optimized to generate substantial EOF and enough chromatographic interactions.

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